Carbonylic compounds containing the sf5 function



United States Patent 3,102,903 CARBONYLIC COMPOUNDS CONTAINING THE SE FUNCTION Donald D. Colfrnan, West Chester, Pa., and Charles W.

Tullock, Wilmington, Del., assignors to E. I. du Pont de Nernours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Oct. 31, 1961, Ser. No. 148,817

8 Claims. (Cl. 260-481) This invention relates to, and has as its principal objects provision of, novel compositions of matter containing the SF function and the preparation of the same.

Our copending application, Serial No. 92,179, filed February 28, 1961, discloses and claims a one-step synthesis of SF Cl which consists in reacting chlorine with sulfur tetrafiuoride and a fluoride of a metal of group I of the periodic system having an atomic number of 11 to 55. There are now provided novel derivatives of SF Cl which may be generically described by Formula I:

srn-b-h-X in which R and R are hydrogen or alkyl groups of up to 19 carbons, preferably of up to 7, and X is hydrogen, hydroxyl, chlorine, aryloxy of up to 14 carbons, preferably of up to 7, alkoxy or alkyl of up to 19 carbons, preferably of up to 7, or NAB, in which one or both of A and B are hydrogen or hydrocarbon radicals, particularly alkyl of up to 19 carbons, aryl of up to 14 carbons, or cycloalkyl of up to 8 carbons, and N is nitrogen.

The compounds of Formula I in which R and R are alkyl or hydrogen and X is alkyl are obtained by reacting SF Cl with an a-alkyl substituted vinyl organic ester in accordance with the equations:

in which one or both of Rand R are hydrogen or alkyl of up to 19 carbon atoms, preferably of up to 7 carbon atoms, and R" and X are alkyl of up to 19 carbon atoms, preferably of up to 7 carbon atoms. Examples of a-alkyl substituted vinyl organic esters usable in this process are those in which the alkyl substituent is of up to 19 carbon atoms, particularly of up to 7 carbon atoms, such as (a-methyDvinyl acetate, (a-butyl)vinyl propionate, (cc-heXYDVlIlYl acetate, (a-decyDvinyl butyrate, (cc-d0- decyl)vinyl octanoate, (a-octadecyDvinyl caproate, meth ly-a-propenyl acetate, methyl-a-isobutenyl butyrate, methyl-a-methyl-oc-propenyl heptanoate, rnethyl-a-methyl-isobutenyl stearate, and the like.

In accomplishing the reaction of SF Cl with the a-alkyl substituted vinyl organic ester, a pressure reactor is charged with the ester, cooled to between 70 C. and 80 C., evacuated, and then charged with the SF'EJCI. The quantities of reactants employed are usually equimolar although in some instances the ester is used in excess. After being charged, the reactor is closed and the charge is maintained between -19 C. and 175 C. under autogenous pressure with agitation for from ten minutes to six hours. The reaction mixture is removed from the reactor and the desired product isolated by fractional distillation or other method known to those skilled in the art.

As noted, the reaction between SF Cl and the ester may be carried out at temperatures of from 19 C. to 175 C. Generally, however, temperatures in the range 3,102,903- Patented Sept. 3, 1963 of 20 to C. are used because within this range the best yields of desired products, with good reaction rates, are realized.

The reaction is usually conducted in a closed reactor constructed of material inert to reactants and reaction products. Reactors made from various nickel-ironrnolybdenum alloys are commercially available and are quite suitable. The size of the reactor is not critical, the particular size used being dependent upon the amounts of reactants.

Autogenous pressures are satisfactory. If desired, however, the reaction can be conducted under externally ap plied pressures. Such pressures generally have no practical advantage :but complicate equipment design. In some cases, in fact, reaction occurs at atmospheric pressure and the reflux temperature of SEQ (-19" C.).

The time of reaction is variable and can range from a few minutes to several hours. In some instances after reaction is seemingly complete, it is desirable to permit the reaction mixture to stand at ambient temperatures for periods of time up to 48 hours.

A reaction medium is not essential but is used in some cases because it brings about better contact between the reactants and acts as a moderator for the reaction. Suitable media are those which are normally liquid and inert to the reactants and reaction products. Such media include perhalocarbons, e.g., carbon tetrachloride, trichlorofluoromethane and 1,1,2-trichloro-1,2,2-trifluoroethane, and the like. The amount of any reaction medium used is not critical and can equal or exceed by many fold the combined weight of the reactants.

Formylalkylsulfur pentafluorides, i.e., compounds of Formula I in which X is hydrogen, are obtained by react ing as a precursor a 1:1 molar adduct of SF CI and one of certain vinyl organic esters with an alkali metal hydroxide, preferably sodium or potassium hydroxide, in the presence of a monohydric alcohol or a glycol. Any liquid monohydric alcohol or glycol is suitable in this reaction. The add-ucts employed as precursors are those of SF Cl and vinyl organic esters carrying a hydrogen in the a-position, i.e., vinyl organic esters having the formula wherein R, R and R have the previously assigned definitions. These precursors are prepared by direct interaction of SEQ and the vinyl organic ester, all as illustrated in Example VI below. Reaction conditions are the same as those for reaction with esters having no hydrogen in the (Jr-position, i.e., the a-alk-ylsubstituted esters discussed above. Vinyl esters suitable for synthesizing these precursors include vinyl formate, vinyl acetate, vinyl butyrate, vinyl caproate, vinyl dodecanoate, vinyl hexadecanoate, vinyl stearate, and the like.

Compounds of Formula I in which Rand R are hydrogen or alkyl and X is chlorine are obtained by reacting SF CI with a ketene according to the equation:

R and R being as above. :In some instances small amounts of the compound 0 SFsCRR/C\ are also produced by this reaction. Examples of ketenes usefully employable in the reaction are ketene, methyl ketene, diniethyl lretene, diethyl ketene, dibutyl lcetene, di-

heptyl ketene, and the like. ing the reaction of SF Cl with a ketene are essentially those of the reaction with an organic vinyl ester and need not be repeated.

The products from the reaction of SFgCl with ketenes are acid chlorides and, as such, serve as precursors of those novel compounds of Formula I in which, respectively, R and 'R are hydrogen or alkyl and X is hydroxyl, alkoxy, aryloxy, or NAB, where -N, A and B have the already indicated meanings. These products are obtained by treating the acid chlorides with water, alcohols, phenols, ammonia or primary or secondary amines.

Acids, i.e., compounds of Formula I where X is hydroxyl, are made by the simple hydrolysis of the acid chloride as illustrated in Example ['11, below.

'Esters, i.e., compounds of Formula I where X is aryloxy or alkoxy, are made by the reaction of the acid chloride with a phenol or an alcohol as illustrated in Example IV. In place of the ethanol of this example, there can be used other alcohols, including propanol, butanol, hexanol, octanol, dodeoanol, octadecanol, ethylene glycol, propylene glycol, glycerol, and the like. Suitable phenols which can be used to prepare esters in which X is aryloxy are phenol, lhydroxy-Z,3-dimethylbenzene, resorcinol, phloroglucinol, l-naphthol, and the like.

The reaction between the alcohol and acid chloride is carried out under anhydrous conditions at reflux, which for the lower molecular weight alcohols and phenols usually involves a temperature below 150 C. The amount of alcohol or phenol used is theoretically the molar equivalent of the acid chloride. If desired, larger amounts of the alcohol or phenol can be used. Although it is not essential, in some instances an acid acceptor is included with the alcohol or phenol and acid chloride in the reaction system. When an acid acceptor is used, the amount employed is that which is required to react with the hydrogen chloride liberated in the reaction. Suitable acid acceptors are tertiary amines, particularly pyridine, alkali metal hydroxides and the like. Instead of the free alcohol or phenol there can be used an alkali metal alcoholate or phenolate.

The amides are the products obtained by reaction of the acid chloride with ammonia or with a primary or secondary amine. These amines may be aliphatic, aromatic, or cycloaliphatic. Suitable aliphatic amines are the alkylmines containing up to 19 carbons. Examples of such amines are methyl, butyl, decyl, and octadecyl amines, diethylamine, dibultylamine, methyldecylamine, and the like. Suitable aromatic amines are the monocarbocyclic amines of up to carbon atoms, e.g., aniline, ethylaniline, tolylamine, xylylamine, and the like. Suitable cycloaliphatic amines are the monocarbocyclic amines of up to 19 carbons, e.g., cyclohexylamine, methylcyclohexylamine, decylcyclohexylamine, and the like.

The amine (or ammonia) and acid chloride react in equirnolar proportions. Usually, however, it is preferred to use an excess of the amine over the theoretical amount so that, the excess acts as an acid acceptor. The amidation is carried out at ambient temperature but since the reaction is exothermic it is best to provide cooling means to moderate the heat of reaction. The reaction is conducted in the presence of a reaction medium which is preferably a solvent for the acid chloride and amine. Diethyl ether. and dipropyl ether are suitable media.

With amines which are normally liquid or solid, it is only necessary to mix solutions thereof with a solution of the acid chloride, and after completion of the addition to reflux the solution for periods of time ranging from 30 minutes to two hours to complete the reaction. With volatile amines, it may be necessary to effect the reaction in a closed reactor to avoid loss of amine.

The examples which follow illustrate but do not limit this invention.

Conditions for accomplish- 4 EXAMPLE 1 Isopropenyl acetate (155 g., 1.55 moles) and SF Cl (112 g., 0.6 9 mole) were heated with agitation at 100 C. for one hour in a 500 ml. nickeLiron-molybdenum alloy pressure reactor at autogenous pressure. The reactor was thereafter allowed to cool and the contents were discharged. From the reaction mixture there was recovered 243 g. of liquid products. Distillation through a spinning band column yielded 29 g. of acetyl fluoride, B.P. 18 to. 30 C., 43 g., B.P. 30 to C., which infrared indicated to be a mixture of acetone and monochloroacetone, and 43 g. of isopropenyl acetate starting material, B.P. 80 to C.

Although acetyl chloride should theoretically have been found among the reaction products, as shown in the equation, actually none was found. It is not known why this should have been so, but it is possible that if any acetyl chloride was formed, it did not survive the reaction conditions used, inasmuch as the only acyl halide isolated was acetyl fluoride.

There remained in the distillation vessel 116 g. of higher boiling product. This product was washed three times, using each time a solution of g. of Na S O .5H O in 300 ml. of water to remove chloroacetone. The emulsion which resulted was broken by addition of methylene chloride. After drying over anhydrous magnesium sulfate, the product was distilled through a spinning band column. There was thus obtained 56 g. of product boiling at 53 to 54 C./47 mm. or at 126 C. under atmospheric pressure. Mass spectrometric analyses indicated the product to comprise 96.5 to 98.5 mole percent of SF CH COCH acetonylsulfur pentafluoride, and 1.5 to 3.5 mole percent of ClOH COCH Gas chromatography indicated the product to contain 98% of SF CH COCH and 2% ClCH COCH The formation of the chloroacetone noted above suggests that the addition of SEQ to isopropenyl acetate also may have occurred in the reverse direction to that which led to the formation of acetonylsulf'ur pentaiiuoride.

.An analytically puresample of the ketone was obtained by washing crude product repeatedly with water until it was free of chemically bonded chlorine. The sample so purified distilled at 54 C./48 mm. and analyzed as follows:

Analysis.-Calcd. for C H F OS: 'C, 19.57; H, 2.72; F, 51.63. Found: C, 20.29; H, 3.09; F, 50.23.

Additional evidence for this structure resulted from the formation of a 2,4 dinitrophenylhydrazone, M.P. 143-145 C., from the reaction with 2,4-dinitrophenylhydrazone. The derivative analyzed as follows:

Analysis.-Calc. for C H F N O 'S: N, 15.38. Found: N, 15.24.

Further evidence for the structure was obtained from the fluorine magnetic resonance, which showed the presence of an SP group. The quintuplet splitting for the CH proton magnetic resonance was taken as evidence for the SF CH grouping. Infrared analysis showed carbon-hydrogen absorption at 3.3 carbonyl absorption at 5.8;t, and SP absorption at 11-12,u. The ketone yielded a positive iodoform test on reaction with iodine: potassium iodide solution in an alkaline medium, which was further proof that the grouping was present.

5 EXAMPLE n Ketene (32 g., 0.76 mole) and 'SF Cl (122 g., 0.75 mole) in 190 ml. of carbon tetrachloride were maintained at 25 C. for 20 hours with agitation in a 500 ml. pressure reactor made of a nickel-iron-rnolybdenum alloy.

From duplicate runs there was obtained on distillation 181 g. of colorless chloroformylmethylsulfur pentafluoride, BI. 47 to 48 C./97 mm., 102 C., at atmospheric pressure. Fluorine magnetic resonance showed the presence of an SF group; the proton magnetic resonance spectrum indicated one type of hydrogen, which was split into a quintouplet. This is taken as evidence of the presence of the SF CH group. Infrared analysis showed C--H absorption at 3.36 1 and 3.34 C=O at 556 and strong SP absorption at 11 to 12 Analysis of the product gave the following results:

Analysis.-Calcd. for C H ClF OS: C, 17.36; F, 46.45. Found: C, 17.69; F, 46.05.

The above experiment was repeated, operating at atmospheric pressure under reflux conditions. Under these conditions SF CH COCl was obtained in about 10% conversion, based on the SF Cl charged to the reactor.

EXAMPLE In SF CH COC1+H Oe SF CH CO H+HCl Thirty-five grams of the SF CH COCI, prepared as in Example 11, was added at 24 C. with stirring to 85 ml. of water over a 33-minute period, during which the temperature of the reaction rose to 47 C. Stirring was continued for an additional 20 minutes to complete the reaction. The product was extracted with methylene chloride and dried over magnesium sulfate. Upon removal of the methylene chloride there remained 27 g. of white crystalline carboxyrnethylsulfur pentafluoride, SF CH COOH, which sublimed at 35 to 46 C./0.3 mm. to give 22 g. (a 69% conversion, based on the SF CH COCl) of product melting at 62 to 64 C. The SF CH COOH was readily crystallized from carbon tetrachloride solution. Nuclear magnetic resonance (fluorine) showed that an SP group was present, and the proton spectrum indicated the presence of an acidic hydrogen atom. There was also another hydrogen atom which was split into a quintuplet, indicating the presence of an SF CH grouping. Infrared analysis showed the presence of carboxyl by absorption in the 3p. and 5.8 region, and of an SP group by absorption in the 11 to 12 region. The product analyzed as follows:

Analysis.-Calcd. for (1 11 1 3: F, 51.08; NE, 186. Found: F, 50.54; N.E., 185.4.

EXAMPLE IV SF CH COCl+ C H OH+ SF CH CO C H +HCI A solution of 14 g. of SF CH COCl, prepared as in Example II, in 28 ml. of absolute ethyl alcohol was refluxed for five hours and thereafter distilled. There was obtained 8 g. (which corresponds to a 55% conversion,

.based on the SF CH COCl charged) of colorless ethoxyempirical formula SF5C4H7O2.

Analysis.-Calcd. for C H F O S: F, 44.39; S, 14.95. Found: F, 43.51; S, 14.98.

6 EXAMPLE v To a solution of 10.2 g. of SF CH COCI, prepared as in Example II, in 25 ml. of anhydrous diethyl ether there was added, with stirring, a solution of 9.3 g. of aniline in 25 ml. of anhydrous diethyl ether at 24 C. During the addition the temperature rose to 32 C. After completion of the addition, the mixture was heated to reflux, held at reflux for one hour, and the reaction mixture was then allowed to stand at ambient temperature overnight. The aniline hydrochloride was removed by filtration, and the filtrate was then distilled to remove the diethyl ether. The residue was a light brown solid which weighed 12 g. This corresponds to a conversion of 92%, based on the weight of the SF CH COCI charged. An aliquot portion of the solid anilide was purified by crystalizing three times from solution in hot carbon tetrachloride. The purified (phenylcarbarmoyl)methylsulfur pentafluoridemelted at 114 to 116 C. The infrared spectrum of the solid was very similar to that of acetanilide, except that. it showed strong absorption in the 11 to 12 region, which is indi cative of the SP group. I

Analysis.--Calcd. for C H F NOS: F, 36.40; S, 12.26. Found: F, 35.11; S, 12.62.

EXAMPLE VI 0 CHaOH sF oHioH01oii-oI-I3 2KOH L (onion):

SF CHzOHO-XH2O CH3CO2K KCI SF5CH2CHO'XH2O P205 SFsCHzCHO (a) Methanol Procedure To a solution of 50 g. of

o SF5CH2CHC1O yJ-OHa prepared as described subsequently, in 100ml. of methanol in a 1-liter round bottom flask was added over a period of 38 minutes a solution of 26.5 g. of potassium hydroxide in 250 ml. of methanol, during which time the temperature of the reaction mixture was maintained at 15 to 28 C. by cooling in an ice bath. After completion of the addition of the potassium hydroxide solution, the ice bath was removed, and the reaction mixture was stirred for five hours at 25 C. Thereafter the reaction mixture was filtered to remove the solid product which had separate-d. On standing overnight, a small amount (1.26 g.) of solid material had formed. It was removed by filtration. The filtrate was then subjected to distillation through a spinning band column. The product which distilled at 35 to 41 C./ mm. separated into an upper layer (6 g.), which was chiefly water, and a lower layer (16 :g.), which was identified as SF CH CHO-XH O. Infrared analysis of the aldehyde hydrate showed strong absorption at 2.9, for OH and no absorption in the carbonyl region. The contents of the cold trap (6 g.) and the 16 g. of SF CH CHO-XH O were added with cooling to 16 g. of phosphorus pentoxide. The product was removed by gentle warming under 1 mm. pressure to obtain 11 g. of formylrnethylsulfur pentafluoride, SF CH CHO. Infrared analysis of this product showed strong absorption at 5.75 for carbonyl and only very r weak absorption in the 2.9 1 region for hydroxyl which resulted from the inadvertent addition of traces of water. The infrared absorption pattern for this product was identical with that of an analytically pure sample of SF CH CHO.

(lb) Ethylene Glycol Route To a solution of 75 g. of

s rsonzonoioii-ona in 75 ml. of ethylene glycol there was added at 25 C.,

7 with stirring, a solution'of 36 g. of 85% potassium hydroxide in 300 ml. of ethylene glycol over a period of 99 minutes, during which time the temperature rose to 45 C. Stirring was continued without external heating for an additional six hours. After standing for about 48 hours .(week end), the contents were filtered, and the filtrate was distilled under reduced pressure. When 3 g. of ethylene glycol had distilled over at 50 C./2 mm., the contents of the trap cooled with liquid nitrogen were examined. The upper layer was found to weigh 13.4 g. and appeared to be primarily water, while the 6.5 g. in the lower layer appeared to be SF CH CHO-XH O. Distillation was accordingly continued at 65 to 70 C./2 mm., and an additional 22 g. of crude SF CH CHO-XH O was collected in the trap cooled with liquid nitrogen. Although the aldehyde hydrate distills at a much lower temperature than ethylene glycol, separation of the two was eifected only by distillation of the ethylene glycol, during which the more volatile aldehyde was concentrated in the liquid nitrogen-cooled trap. To an aliquot of the crude SF CH CHO-XH O there was added phosphorus pentoxide with cooling, and the volatile product was re- 'moved by gentle warming under 1 mm. pressure. The residue was found to have a B'.P. of 38 C./98 mm.

Analysis.Calcd. for C H F OS: C, 14.12; H, 1.77; F, 55.90; S, 18.83. Found: C, 14.71; H, 2.17; F, 55.74; S, 19.20.

Infrared analyses showed strong absorption at 3.6;]. for CH, 5.75 4 for CO, and no absorption corresponding to Fluorine magnetic resonance showed the presence of an SF group and the proton resonance spectrum indicated at least two different hydrogens with the CH present as a quintuplet, which is indicative of the SF CH group.

Gas chromatography, using a 1 meter column packed with finely divided diatomaceou-s earth treated with 20% by weight of a silicone oil at 72 C. and a flow rate of 90 cc./minute showed that only one product was present.

The above data, taken with the fact that the product formed a semicarbazone, M.P. 122124 C., whose infrared spectrum is consistent for are corroborative of the structure as being SF CH CHO.

The

ll SF5CHzCHClOCCHs used in the above experiments was prepared as follows:

Fifty-two grams of redistilled monomeric vinyl acetate, B.P. 72 C., and 58 -g.' of SF Cl were heated with stirring at 50 C. for one hour in a nickel-iron-molybdenum pressure reactor. The reactor was thereafter allowed to cool and was opened. There was recovered 7 g. of gaseous product, shown by infrared to be a mixture of SOF SF Cl, and CH COF, and 103 g. of liquid product. Distil-lation of the liquid yielded 71 g. of material boiling at 36 C./2.7 mm. This corresponds to an 83.5% conversion, based on the SF Cl charged. Gas chromotographic analysis showed that the product contained only one matetrial. Elemental analysis (chlorine, fluorine and sulfur) indicated that a 1:1 molar adduct of SF Cl and vinyl ace- 'tate had been obtained. This, together with the chemical evidence resulting from the synthesis of formylmethylsulfur pentafluoride from it (Example VI), indicated that the product was Anhydrous gaseous ammonia (7 g.) was added over a period of 23 minutes to a stirred solution of 21 g. of

prepared as in Example II, in ml. of anhydrous diethyl ether, cooled in an ice bath, during which the temperature rose from +1 C. to 22 C. and then dropped to 15 C. The solid (16 g.), a mixture of was suspended in 65 ml. of dioxane; 4.4 g. of NH Cl remained insoluble. Concentration of the dioxane solution yielded 11 g. of amide; recrystallization of this from hot benzene yielded 7 g. of

MP. 143-144 C. The compound, carboxamidomethylsulfur pentafluoride, was shown by nuclear magnetic resonance (fluorine) analysis to contain an SP group. Infrared analysis showed NH absorption at 2.9 (b-O at 5.9,u, and SF by strong absorption in the 11 to 12 4 region.

Concentration of the ether solution in which the reaction was carried out yielded an additional 4 g. of crude carboxamidomethylsulfur pentafluoride,

Analysis.Calcd. for C H F5NOS: C, 12.97; H, 2.16; F, 51.35; S, 17.30. Found: C, 13.54; H, 2.41; F, 50.43; S, 17.10.

The products of this invention are useful intermediates in chemical syntheses and as solvents for polymeric material. Thus, the aldehyde hydrate, prepared as in Example VI, swells the polyamide from hexamethyleneadipamide in the cold and is an active solvent for this polyamide and for Delrin acetal resin in the hot, and the acid, obtained as in Example III, is stronger than acetic acid. At temperatures above its melting point, the acid is an active solvent for the polyamide from hexamethyleneadipamide, forming solutions which do not crystallize on cooling. These solutions are eminently useful for forming films, fibers, and the like of polyamides.

Since obvious modifications and equivalents in the invention will be evident to those skilled in the chemical arts, we'p-ropose to be bound solely by the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula SF5(:J(LJ-X RI wherein: R and R are selected from the group consisting of hydrogen and alkyl of up to 19 carbons; and X is se- 9 16 lected from the group consisting of hydrogen, hydroxyl, References Cited in the file of this patent chlorine, aryloxy of up to 14 carbon atoms and alkyl and UNITED STATES PATENTS alkoxy of up to 19 carbon atoms and NAB, A and B 2 859 245 smith NOV 4 1958 being members of the group consisting of hydrogen and 7 w alkyl of up to 19 carbons, aryl of up to 14 carbons and 5 OTHER REFERENCES cycloalkyl of 8 carbons- Roberts et aL: J. Chem. Soc. (London), 1960, pp.

. The compound of the formula SF CH COCH 5 57 The compound of the formula s z Case et a1.: 1. Chem. Soc. (London), 1961, pp. 2066- The compound of the formula. SF CH COOH. 2075 Th6 compound of H16 formula 5 2 2 5- 1O Pattison et -al.: Journal of Organic Chemistry, vol. 21, The compound of the formula SF CH CONHC H N0- PP- 837889 (August The compound of the formula SF CH CHO. Wagner and Zook: Synthetic Organic Chemistry, Jolm The compound of the formula SF CH 'CONH Wiley & Sons, Inc., New York, pp. 418, 481-482 and 566. 

1. A COMPOUND OF THE FORMULA 